CN108003848A - Supramolecular materials and preparation method thereof and the application in without native phase water-base drilling fluid as extracting and cutting agent - Google Patents
Supramolecular materials and preparation method thereof and the application in without native phase water-base drilling fluid as extracting and cutting agent Download PDFInfo
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- CN108003848A CN108003848A CN201711345803.0A CN201711345803A CN108003848A CN 108003848 A CN108003848 A CN 108003848A CN 201711345803 A CN201711345803 A CN 201711345803A CN 108003848 A CN108003848 A CN 108003848A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
- C09K8/03—Specific additives for general use in well-drilling compositions
- C09K8/032—Inorganic additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
- C09K8/04—Aqueous well-drilling compositions
- C09K8/05—Aqueous well-drilling compositions containing inorganic compounds only, e.g. mixtures of clay and salt
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- E—FIXED CONSTRUCTIONS
- E21—EARTH DRILLING; MINING
- E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B21/00—Methods or apparatus for flushing boreholes, e.g. by use of exhaust air from motor
Abstract
The present invention relates to oil/gas drilling field, and in particular to supramolecular materials and preparation method thereof and the application in without native phase water-base drilling fluid as extracting and cutting agent.The supramolecular materials are by CaO, C, SiO2It is combined into with reference to water.When supramolecular materials provided by the invention are used as extracting and cutting agent in water-base drilling fluid, it can obtain preferable carry in the case where not using other clays and cut effect, it shows low viscosity under high shear conditions；And high viscosity is shown under low shear conditions, beneficial to bit speed is improved, acquisition takes rock by force with good thixotropic without native phase water-base drilling fluid.
Description
Technical field
The present invention relates to oil/gas drilling field, and in particular to supramolecular materials and preparation method thereof with without the mutually water base brill of soil
Application in well liquid as extracting and cutting agent.
Background technology
Horizontal well is as a kind of Efficient Development well type, by increasing capacitance it is possible to increase the contact area of pit shaft and reservoir, is adopted improving oil well
There is remarkable result in terms of yield.Horizontal segment carries drilling cuttings difficulty during horizontal well drilling, and easily formation cutting bed, which adds, rubs
Resistance, moment of torsion, or even the accidents such as bit freezing are caused, seriously affect drilling efficiency.Therefore, drilling fluid must have takes lithology energy well,
This rheological characteristic to drilling fluid proposes higher requirement.Water-base drilling fluid with its environmental protection, it is inexpensive the characteristics of and made extensively
With being mainly made of bentonite, various polymer and weighting material.Lithology energy is preferably taken to realize, is led in water-base drilling fluid
Substantial amounts of bentonite and polymer are commonly incorporated into, and this can reduce rate of penetration and form thicker filter cake, cause to stick bit freezing
Etc. accident.Therefore, develop efficiently take the strong thixotroping of rock without clay water base drilling fluid system improve bit speed, solve horizontal well
Take rock problem, it appears it is very necessary, and efficiently extracting and cutting agent is the key of the water base drilling fluid system.
At present, the water-base drilling fluid extracting and cutting agent researched and developed both at home and abroad is deposited monomer used in the synthesis process more and not environmentally, is synthesized
Complex process, product cost are higher, it is difficult to the problems such as large-scale application.In addition, the polymer extracting and cutting agent of these synthesis is in drill bit
At hydrophthalmia there is the possibility for being sheared degraded in (high-rate of shear), and influence drilling speed, it is difficult to obtain the high water base brill of large rock-carrying ability
Well liquid system.
The content of the invention
There is good thixotropy it is an object of the invention to provide one kind and shear force height is obtained under less dosage, takes rock energy
High supramolecular materials without native phase water-base drilling fluid of power and preparation method thereof and cut in without native phase water-base drilling fluid as carrying
The application of agent.
The present inventor, which furthers investigate, to be found, supramolecular materials of the invention being capable of hydrogel under high shear conditions
Structure is broken, and shows low viscosity；And under low shear conditions, hydrogel structure recovers again, shows high viscosity, thus
During as water-base drilling fluid extracting and cutting agent, bit speed can be improved, acquisition takes rock by force with good thixotropic mutually water base without soil
Drilling fluid.
For this reason, one aspect of the present invention provides a kind of supramolecular materials, the supramolecular materials are by CaO, C, SiO2With with reference to water
It is combined into.
Second aspect of the present invention provides a kind of preparation method of supramolecular materials, and this method includes：
(1) in aqueous solvent, and in alkaline conditions, calcium source, carbon source and silicon source are mixed；
(2) mixing gained mixture is aged, then carries out separation of solid and liquid, and dry gained solid phase；
Wherein, the calcium source is calcium oxide and/or calcium hydroxide, and the carbon source is graphite, graphene, graphite oxide and oxygen
One or more in graphite alkene, the silicon source are silica；
The condition of the ageing includes：Temperature is more than 100 DEG C, and the time is more than 10h.
Third aspect present invention provides the supramolecular materials as made from the method described in second aspect.
Fourth aspect present invention provides application of the above-mentioned supramolecular materials in drilling fluid as extracting and cutting agent.
Fifth aspect present invention provides a kind of water-base drilling fluid containing in above-mentioned supramolecular materials as extracting and cutting agent.
Sixth aspect present invention provides application of the above-mentioned water-base drilling fluid in oil/gas drilling.
When supramolecular materials provided by the invention are used as extracting and cutting agent in water-base drilling fluid, other clays can not used
Under, obtain preferable carry and cut effect, it shows low viscosity under high shear conditions；And show under low shear conditions high viscous
Degree, beneficial to bit speed is improved, acquisition takes rock by force with good thixotropic without native phase water-base drilling fluid.
Brief description of the drawings
Fig. 1 is the TEM figures for the aggregation that the supramolecular materials obtained by the present invention are formed in water.
Embodiment
The endpoint of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of a scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
One aspect of the present invention provides a kind of supramolecular materials, and the supramolecular materials are by CaO, C, SiO2With with reference to water with reference to and
Into.
According to the present invention, supramolecular materials of the invention are by CaO, C, SiO2It is combined into, is also considered as described with reference to water
Supramolecular materials are by CaO, C, SiO2(retouched with water is combined by being chemically bonded to be combined into intermolecular force in following article
The high temperature ageing process stated, also can be described as supramolecular materials by CaO, C, SiO2With with reference to water by way of Hydrothermal Synthesiss and
It is bonded to each other and is made), intermolecular force can be passed through in water between the supramolecular materials and form supramolecular aggregation, i.e. shape
The hydrogel reversible into structure, is thus known as supramolecular materials.
In accordance with the present invention it is preferred that in the supramolecular materials, CaO, C and SiO2Molar ratio be 1：0.05-2：0.1-
5, it is preferably 1：0.1-1.5：0.5-3, more preferably 1：0.15-1：0.8-2, is still more preferably 1：0.4-0.8：1.2-
1.8。
Wherein, can be changed with reference to the content of water in relative broad range, such as the molar ratio of CaO and combination water is 0.01
More than, it is preferably more than 0.05, more preferably more than 0.1, it is still more preferably 0.1-10, is, for example, 0.1-1.
In a kind of preferred embodiment of the present invention, the supramolecular materials are by formula CaOxCySiO2·mH2O
It is represented, wherein, x 0.05-2, are preferably 0.1-1.5, more preferably 0.15-1, are still more preferably 0.4-0.8；Y is
0.1-5, is preferably 0.5-3, more preferably 0.8-2, is still more preferably 1.2-1.8；M is more than 0.01, is preferably 0.05
More than, more preferably more than 0.1, it is still more preferably 0.1-10, is, for example, 0.1-1.
According to the present invention, the supramolecular materials will form the aggregation of multiple supramolecular materials in water, in low sheraing
In condition, such aggregation will not scatter, will in aggregation as high shear to improve system viscosity and large rock-carrying ability
Single supramolecular materials or smaller size of aggregation are divided into, is easy to be pumped into shaft bottom rapidly, obtains more preferable waterpower
Rock breaking efficiency.The supramolecular materials are by CaO, C, SiO2Obtained with combining water and combining, it is with certain granularity, preferably
Ground, the particle mean size of the supramolecular materials (i.e. single supramolecular materials) is 10-100nm, is preferably 20-50nm.
Second aspect of the present invention provides a kind of preparation method of supramolecular materials, and this method includes：
(1) in aqueous solvent, and in alkaline conditions, calcium source, carbon source and silicon source are mixed；
(2) mixing gained mixture is aged, then carries out separation of solid and liquid, and dry gained solid phase；
Wherein, the calcium source is calcium oxide and/or calcium hydroxide, and the carbon source is graphite, graphene, graphite oxide and oxygen
One or more in graphite alkene, the silicon source are silica；
The condition of the ageing includes：Temperature is more than 100 DEG C, and the time is more than 10h.
According to the present invention, the dosage of the calcium source, carbon source and silicon source can be according to the composition in required supramolecular materials
Suitably adjusted, it is preferable that the calcium source in terms of CaO, the carbon source in terms of C and with SiO2The molar ratio of the silicon source of meter is 1：
0.05-2：0.1-5, is preferably 1：0.1-1.5：0.5-3, more preferably 1：0.15-1：0.8-2, is still more preferably 1：
0.4-0.8：1.2-1.8.
In a kind of preferred embodiment of the present invention, the calcium source is calcium oxide, and the carbon source is graphite, the silicon
Source is silica.Wherein, calcium oxide preferably uses calcium oxide powder, its granularity is 1-10 μm；Graphite preferably uses graphite powder, its
Granularity is 5-15 μm；Silica preferably uses silicon dioxide powder, its granularity is 1-10 μm.
According to the present invention, the aqueous solvent can be water or not influence the supermolecule of the present invention containing other
The mixture of the water for the solvent that material is formed, is preferably water.Wherein, the dosage of the aqueous solvent can become in relative broad range
It is dynamic, it is preferable that relative to the calcium source in terms of CaO of 100mmol, the carbon source in terms of C and with SiO2Total dosage of the silicon source of meter, institute
The dosage for stating aqueous solvent is 100-500mL, more preferably 200-400mL.
In the case of, according to the invention it is preferred to, the pH of the alkaline condition is 8.5-11, is preferably 9-10.Such alkalescence
Condition can be realized by the alkaline system control system of this area routine, such as can be by buffer salt to realizing, example
Such as sodium hydroxide solution and the buffer solution of sodium acid carbonate.
According to the present invention, the mixing of step (1) can make it that calcium source, carbon source and silicon source are fully dispersed, wherein, the mixing
Condition include：Under the mixing speed of 500-1000rpm, 10-60min is stirred；Preferably, stirring in 600-800rpm
Mix under speed, be stirred 20-40min.
According to the present invention, mixture obtained by step (1) is aged by step (2), can make mutually reciprocal between raw material
Should, to form specific crystal structure, thus obtain the supramolecular materials structure of the present invention.Wherein, the ageing is preferably close
In closure system, carried out under static conditions.
Under preferable case, the condition of the ageing includes：Temperature is 120-200 DEG C, time 15-30h.It is highly preferred that
The condition of the ageing includes：Temperature is 150-180 DEG C, time 20-26h.
Product after ageing is subjected to separation of solid and liquid (such as mode of centrifugation), and gained solid phase is washed, it is dry
(such as drying 0.5-3h at 50-80 DEG C), can then be ground to obtain supramolecular materials.
Third aspect present invention provides the supramolecular materials as made from the method described in second aspect.
It should be appreciated that supramolecular materials made from this method can be as described above supramolecular materials, but
As long as it is to be included in using material made from this method in the third aspect.
Fourth aspect present invention provides application of the above-mentioned supramolecular materials in drilling fluid as extracting and cutting agent.
When the supramolecular materials of the present invention are used as extracting and cutting agent in drilling fluid, there is good thixotropy, not only have and carry
The ability of high drilling speed, improves the effect of shear force, but also can show good inhibition, can suppress the aquation of shale
Scattered, expansion migration etc..Wherein, thixotropy here refers to showing low viscosity effect under high shear, is showed under low sheraing
Go out high viscosity effect.
Fifth aspect present invention provides a kind of water-base drilling fluid containing in above-mentioned supramolecular materials as extracting and cutting agent.
According to the present invention, the supramolecular materials can be used in water-base drilling fluid as extracting and cutting agent, and can be less
Under additive amount, obtain the thickening same with more clays and put forward the effect cut, for this reason, can not be adopted in the water-base drilling fluid of the present invention
Cut with clay to viscosify to carry, it is thus preferable to, the water-base drilling fluid is without native phase water-base drilling fluid.
According to the present invention, the supramolecular materials can obtain excellent thickening and carry and cut effect, preferably under lower content
Ground, the content of the supramolecular materials is 1-2 weight %, on the basis of the gross weight of the water-base drilling fluid.
In addition, the drilling fluid of the invention as water-base drilling fluid can also be used for water-based drilling containing this area routine
Additive in liquid, for example, on the basis of the gross weight of water-base drilling fluid, can the temperature resistance filtrate reducing containing 0.1-1 weight %
Agent (such as can be modified sodium humate condensation polymer (KJAN), phenolic resin, sulfonated-pheno-formoldehyde resin, sulfonated-methyl brown coal tree
One or more in fat etc.), salt resistant filter loss reduction agent (cellulose ether derivatives (PAC), starch, the modification of 0.5-2 weight %
One or more in starch and carboxymethyl cellulose etc.), the sealing agent of 0.5-2 weight % (such as calcium carbonate superfine powder, white drip
One or more in blue or green, commercially available sealing agent ZHFD-1 etc.), and heavy weight additive (such as can be that barite (such as can be
Barite of the barium sulfate content more than 90 weight %), organic salt (weigh-1, weigh-2 (active ingredient is potassium formate),
Weigh-3, Organic Sodium Salt GD-WT) etc. in one or more) so that water-base drilling fluid obtain needed for density, be, for example, 1-
3g/cm3。
Sixth aspect present invention provides application of the above-mentioned water-base drilling fluid in oil/gas drilling.
The water-base drilling fluid of gained of the invention, can obtain in the case of without native phase, under less extracting and cutting agent dosage
Excellent drilling speed, can be that one kind takes rock by force with good thixotropic without native phase water-base drilling fluid.
The present invention will be described in detail by way of examples below.
In example below：
Calcium oxide powder is purchased from An Naiji chemical companies, its granularity is about 5 μm；Graphite powder is purchased from Aladdin company, its granularity
About 10 μm；Silicon dioxide powder is purchased from An Naiji chemical companies, its granularity is about 2 μm.
Microstructure and component composition use the Tecnai G of FEI Co. of the U.S.2F20 model transmission electron microscopes
(TEM) measure.
The particle diameter distribution of supramolecular materials is measured using Malvern company of Britain Zetasize Nano ZS Particle Size Analyzers.
Embodiment 1
The present embodiment is used to illustrate supramolecular materials of the present invention and preparation method thereof.
(1) by calcium oxide powder, graphite powder and silicon dioxide powder, (molar ratio of calcium oxide, graphite and silica is 1：
0.75：1.6, total amount 100mmol) it is added in the water of 200mL, then pass through sodium hydroxide and sodium bicarbonate buffer solution tune
PH is to 10 for section system, and is stirred 30min at 800 rpm；
(2) mixture is transferred in closed reaction vessel, and the still aging 24h at 180 DEG C, then centrifuge, institute
Solid phase is obtained to be washed with water, and for dry 1h to drying, grinding obtains supramolecular materials A1 at 60 DEG C, wherein, CaO, C, SiO2With
Molar ratio with reference to water is 1：0.75：1.6：0.1.
The supramolecular materials of gained are dispersed in water, by tem observation (see figure 1), the supramolecular materials are in water
Three-dimensional netted aggregate structure is presented in aggregation each other for middle formation；The flat of the supramolecular materials is measured using laser particle size analyzer
Equal granularity is 30nm.
Embodiment 2
The present embodiment is used to illustrate supramolecular materials of the present invention and preparation method thereof.
(1) by calcium oxide powder, graphite powder and silicon dioxide powder, (molar ratio of calcium oxide, graphite and silica is 1：
0.65：1.3, total amount 200mmol) it is added in the water of 200mL, then pass through sodium hydroxide and sodium bicarbonate buffer solution tune
PH is to 9.5 for section system, and is stirred 40min under 650rpm；
(2) mixture is transferred in closed reaction vessel, and the still aging 20h at 170 DEG C, then centrifuge, institute
Solid phase is obtained to be washed with water, and for dry 1h to drying, grinding obtains supramolecular materials A2 at 60 DEG C, wherein, CaO, C, SiO2With
Molar ratio with reference to water is 1：0.65：1.3：0.2.
The supramolecular materials of gained are dispersed in water, by tem observation, which forms in water gathers each other
Three-dimensional netted aggregate structure is presented in collection；Use laser particle size analyzer measure the particle mean sizes of the supramolecular materials for
40nm。
Embodiment 3
The present embodiment is used to illustrate supramolecular materials of the present invention and preparation method thereof.
(1) by calcium oxide powder, graphite powder and silicon dioxide powder, (molar ratio of calcium oxide, graphite and silica is 1：
0.28：1.1, total amount 150mmol) it is added in the water of 200mL, then pass through sodium hydroxide and sodium bicarbonate buffer solution tune
PH is to 9.5 for section system, and is stirred 30min under 700rpm；
(2) mixture is transferred in closed reaction vessel, and the still aging 25h at 150 DEG C, then centrifuge, institute
Solid phase is obtained to be washed with water, and for dry 1h to drying, grinding obtains supramolecular materials A3 at 60 DEG C, wherein, CaO, C, SiO2With
Molar ratio with reference to water is 1：0.28：1.1：0.25.
The supramolecular materials of gained are dispersed in water, by tem observation, which forms in water gathers each other
Three-dimensional netted aggregate structure is presented in collection；Use laser particle size analyzer measure the particle mean sizes of the supramolecular materials for
50nm。
Embodiment 4
The present embodiment is used to illustrate supramolecular materials of the present invention and preparation method thereof.
According to the method described in embodiment 1, the difference is that, the dosage of calcium oxide powder, graphite powder and silicon dioxide powder causes
The molar ratio of calcium oxide, graphite and silica is 1：0.15：0.9, total amount is constant to remain as 100mmol；
Supramolecular materials A4 is finally obtained, wherein, CaO, C, SiO2It is 1 with the molar ratio for combining water：0.15：0.9：0.2.
The supramolecular materials of gained are dispersed in water, by tem observation, which forms in water gathers each other
Three-dimensional netted aggregate structure is presented in collection；Use laser particle size analyzer measure the particle mean sizes of the supramolecular materials for
50nm。
Embodiment 5
The present embodiment is used to illustrate supramolecular materials of the present invention and preparation method thereof.
According to the method described in embodiment 1, the difference is that, the dosage of calcium oxide powder, graphite powder and silicon dioxide powder causes
The molar ratio of calcium oxide, graphite and silica is 1：1.5：2.5, total amount is constant to remain as 100mmol；
Supramolecular materials A5 is finally obtained, wherein, CaO, C, SiO2It is 1 with the molar ratio for combining water：1.5：2.5：0.4.
The supramolecular materials of gained are dispersed in water, by tem observation, which forms in water gathers each other
Three-dimensional netted aggregate structure is presented in collection；Use laser particle size analyzer measure the particle mean sizes of the supramolecular materials for
30nm。
Comparative example 1
By calcium oxide powder, graphite powder and silicon dioxide powder, (molar ratio of calcium oxide, graphite and silica is 1：0.75：
1.6, total amount 100mmol) it is ground and mixes with the water of 5mL, then dry and grind to obtain inorganic material DA1.
Test case 1
Above-mentioned supramolecular materials A1-A5 and inorganic material DA1 are dispersed in water respectively, corresponding moisture is obtained and dissipates
Liquid, and it is 2 weight % to control its concentration；And bentonite (sodium bentonite for being purchased from Weifang Hua Wei bentonites Co., Ltd) is divided
Dissipate in water, the aqueous dispersions that bentonite content is 4 weight %, 6 weight % and 8 weight % are made respectively；To such moisture
The rheological characteristic and filtrate loss controllability of dispersion liquid are tested, the result is shown in shown in table 1, wherein：
PV refers to plastic viscosity, is measured by the fast viscosimeter of normal form six, unit mPas, PV=θ600-θ300；
AV refers to apparent viscosity, is measured by the fast viscosimeter of normal form six, unit mPas,
Ratio of dynamic shear force/yield value to plastic viscosity=YP/PV；
YP refers to yield value, is calculated by the fast viscosimeter data measured of normal form six, unit Pa, YP=0.511 (θ300-
PV)；
G10"/G10'Refer to gel strength to ingress/egress, be calculated by the fast viscosimeter data measured of normal form six, unit Pa,
API refers to middle filter pressing loss, is committed a breach of etiquette and measured by middle press filtration, unit mL.
Table 1
It can be seen that by the data of table 1 when bentonitic additive amount reaches 4 weight %, its thickening carries what is cut
Effect is only that the thickening of supramolecular materials of 2 weight % carries and cuts effect all far away from the additive amount of the present invention, only works as bentonite
Additive amount when reaching 6 weight %, even 8 weight % or so, the carrying for supramolecular materials that can basically reach the present invention is cut
Effect, but its apparent viscosity and plastic viscosity are again too high, are unfavorable for reducing cyclic pressure dissipation and improve drilling speed.
Test case 2
Above-mentioned supramolecular materials A2 is dispersed in water, it is 1 weight %, 1.5 weight % and 2 weight % to respectively obtain concentration
Aqueous dispersions；Supramolecular materials A1, A3-A5 inorganic material DA1 is dispersed in water respectively, it is 2 weight %'s to obtain concentration
Aqueous dispersions；And be dispersed in water bentonite (sodium bentonite for being purchased from Weifang Hua Wei bentonites Co., Ltd), respectively
The aqueous dispersions that bentonite content is 4 weight %, 6 weight % and 8 weight % are made；Respectively by above-mentioned dispersion liquid unaged
In high-rate of shear (1000s before (25 DEG C of room temperature is placed)-1) under tested viscosity, then again in low shear rate (0.1s-1) under
Tested viscosity；And respectively by above-mentioned dispersion liquid after 150 DEG C of aging 16h again in high-rate of shear (1000s-1) under test it is viscous
Degree, then again in low shear rate (0.1s-1) under tested viscosity；It the results are shown in Table shown in 2.
Table 2
The supramolecular materials that can be seen that the present invention by the data of table 2 are used as extracting and cutting agent to show excellent shearing dilute
The property released, viscosity is high at low shear rates, and viscosity is low at high shear rates.Carried in addition, the supramolecular materials of the present invention are used as
Cut agent viscosity after 150 DEG C of high temperature ageings to be increased slightly, show stronger shear thinning behavior, and the bentonite (8% of high concentration
Bentonite) viscosity sharply increases after high temperature ageing, and in not flowable paste, rheological characteristic drastically deteriorates.
Test case 3
Above-mentioned supramolecular materials A2 is dispersed in water, it is 1 weight %, 1.5 weight % and 2 weight % to respectively obtain concentration
Aqueous dispersions；Supramolecular materials A1, A3-A5 inorganic material DA1 is dispersed in water respectively, it is 2 weight %'s to obtain concentration
Aqueous dispersions；And prepare the potassium chloride solution of 7 weight %；According to professional standard (SY/T 6335-1997) shale inhibition
Evaluation method, measures manually compacting rock core 24h expansion heights using shale expansion tester, evaluates above-mentioned aqueous dispersions, chlorination
The inhibition of aqueous solutions of potassium and clear water；It the results are shown in Table shown in 3.
Table 3
The supramolecular materials that can be seen that the present invention by the data of the table 3 are used as extracting and cutting agent and also show preferably to press down
Effect processed, it can reach the inhibition of the conventional potassium chloride inhibitor of higher additive amount with more few additive.
Test case 4
Above-mentioned supramolecular materials A2 is dispersed in water, the moisture that concentration is 1.5 weight % and 2 weight % is respectively obtained and dissipates
Liquid；Supramolecular materials A1, A3-A5 inorganic material DA1 is dispersed in water respectively, obtains the aqueous dispersions that concentration is 2 weight %；
And be dispersed in water bentonite (sodium bentonite for being purchased from Weifang Hua Wei bentonites Co., Ltd), bentonite is made respectively
Content is the aqueous dispersions of 4 weight % and 6 weight %；The drilling speed of above-mentioned dispersion liquid is tested under following experiment parameter,
It the results are shown in Table shown in 4, wherein, experiment parameter includes：Drilling depth：20cm；Speed setting：80 turns/min；Weight on bit settings：
0.5kN；The pressure of the drill upper limit：0.5kN；Drilling fluid flow velocity：20L/min.
Table 4
| Drilling speed (cm/min) | |
| 1.5% A2 | 3.1 |
| 2.0% A2 | 3.3 |
| 2.0% A1 | 3.2 |
| 2.0% A3 | 3.0 |
| 2.0% A4 | 2.7 |
| 2.0% A5 | 2.8 |
| 2.0% DA1 | 1.8 |
| 4% bentonite | 2.6 |
| 6% bentonite | 2.1 |
By the data of table 4 can be seen that the present invention supramolecular materials be used as extracting and cutting agent when, it is possible to increase power auger
Speed, particularly, when increasing extracting and cutting agent additive amount, drilling speed also accordingly increases.For this reason, contain the supramolecular materials conduct of the present invention
The target efficiently taken bits and improve drilling speed can be achieved at the same time in the water-base drilling fluid of extracting and cutting agent.
Test case 5
Water-base drilling fluid 1#Composition：The supramolecular materials A2 of 1.5 weight % is as extracting and cutting agent, the sulphur first of 0.5 weight %
Base phenolic resin fluid loss additive (is purchased from the SMP-II of Xin Lei oilfield additives Co., Ltd of Xinxiang City, the same below), the envelope of 1 weight %
Blocking agent albino bitumen (is purchased from Henan marine chemical industry Co., Ltd), the starch of 1 weight %, and addition water and barite adjust the brill
The density of well liquid is 1.4g/cm3。
Water-base drilling fluid 2#Composition：Using the composition of water-base drilling fluid 1#, the difference is that, using the swelling of 4 weight %
Soil (sodium bentonite for being purchased from Weifang Hua Wei bentonites Co., Ltd) and 0.15 weight % polyacrylamides sylvite (are purchased from Renqiu
City Hong Ze petrochemical industries Co., Ltd K-PAM) instead of the supramolecular materials A2 of 1.5 weight %.
According to the method for test case 1, to (25 DEG C of room temperatures gained) and the 120 DEG C of agings before ageing of above-mentioned water-base drilling fluid
Rheological characteristic and filtrate loss controllability after 16h are tested, and the result is shown in shown in table 5.
Table 5
The supramolecular materials using the present invention are can be seen that as the 1 of extracting and cutting agent by the data of the table 5#Drilling fluid system is old
Yield value is unchanged before and after change, and first egress is declined slightly but still significantly higher than 2#The first egress of drilling fluid, and with bentonite and gather
Compound (polyacrylamide sylvite) as thickening extracting and cutting agent 2#Drilling fluid system, yield value declines obvious, first egress after aging
In reduced levels, high temperature and pressure leak-off is higher than 1#Drilling fluid system.In addition, after weathering 1#The plastic viscosity of drilling fluid system
Less than 2#Drilling fluid system, but yield value and first egress are much larger than 2#Drilling fluid system, relatively low plastic viscosity, which advantageously reduces, to be followed
Ring pressure consumption, improves drilling speed, higher yield value and first egress are conducive to cutting carring.Therefore, with the supramolecular materials of the present invention
Drilling fluid system for extracting and cutting agent has the function that to improve drilling speed and efficiently takes rock.
The preferred embodiment of the present invention described in detail above, still, the present invention is not limited thereto.In the skill of the present invention
In art concept, technical scheme can be carried out a variety of simple variants, including each technical characteristic with it is any its
Its suitable method is combined, these simple variants and combination should equally be considered as content disclosed in this invention, belong to
Protection scope of the present invention.
Claims (13)
1. a kind of supramolecular materials, it is characterised in that the supramolecular materials are by CaO, C, SiO2It is combined into with reference to water.
2. supramolecular materials according to claim 1, wherein, in the supramolecular materials, CaO, C and SiO2Molar ratio
For 1：0.05-2：0.1-5, is preferably 1：0.1-1.5：0.5-3, more preferably 1：0.15-1：0.8-2, still more preferably for
1：0.4-0.8：1.2-1.8.
3. supramolecular materials according to claim 1, wherein, the supramolecular materials are by formula CaOxCySiO2·
mH2Represented by O, wherein, x 0.05-2, are preferably 0.1-1.5, more preferably 0.15-1, are still more preferably 0.4-0.8；
Y is 0.1-5, is preferably 0.5-3, and more preferably 0.8-2, is still more preferably 1.2-1.8；M is more than 0.01, is preferably
More than 0.05, more preferably more than 0.1, are still more preferably 0.1-10.
4. according to the supramolecular materials described in any one in claim 1-3, wherein, the particle mean size of the supramolecular materials
It is preferably 20-50nm for 10-100nm.
5. a kind of preparation method of supramolecular materials, it is characterised in that this method includes：
(1) in aqueous solvent, and in alkaline conditions, calcium source, carbon source and silicon source are mixed；
(2) mixing gained mixture is aged, then carries out separation of solid and liquid, and dry gained solid phase；
Wherein, the calcium source is calcium oxide and/or calcium hydroxide, and the carbon source is graphite, graphene, graphite oxide and oxidation stone
One or more in black alkene, the silicon source are silica；
The condition of the ageing includes：Temperature is more than 100 DEG C, and the time is more than 10h.
6. according to the method described in claim 5, wherein, the calcium source in terms of CaO, the carbon source in terms of C and with SiO2The silicon source of meter
Molar ratio is 1：0.05-2：0.1-5, is preferably 1：0.1-1.5：0.5-3, more preferably 1：0.15-1：0.8-2, further
Preferably 1：0.4-0.8：1.2-1.8；
Preferably, the calcium source is calcium oxide, and the carbon source is graphite, and the silicon source is silica.
7. the method according to claim 5 or 6, wherein, the calcium source in terms of CaO relative to 100mmol, the carbon in terms of C
Source and with SiO2Total dosage of the silicon source of meter, the dosage of the aqueous solvent is 100-500mL；
Preferably, the pH of the alkaline condition is 8.5-11, is preferably 9-10.
8. according to the method described in any one in claim 5-7, wherein, the condition of the ageing includes：Temperature is 120-
200 DEG C, time 15-30h；
Preferably, the condition of the ageing includes：Temperature is 150-180 DEG C, time 20-26h；
Preferably, the ageing carries out in enclosed system.
9. the supramolecular materials as made from the method described in any one in claim 5-8.
10. application of the supramolecular materials in claim 1-4 and 9 described in any one in drilling fluid as extracting and cutting agent.
A kind of 11. water-based drilling in supramolecular materials containing described in any one in claim 1-4 and 9 as extracting and cutting agent
Liquid.
12. water-base drilling fluid according to claim 11, wherein, the water-base drilling fluid be without native phase water-base drilling fluid,
Preferably, the content of the supramolecular materials is 1-2 weight %.
13. application of the water-base drilling fluid described in claim 11 or 12 in oil/gas drilling.
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